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Publication numberUS3539618 A
Publication typeGrant
Publication dateNov 10, 1970
Filing dateApr 15, 1966
Priority dateApr 15, 1966
Publication numberUS 3539618 A, US 3539618A, US-A-3539618, US3539618 A, US3539618A
InventorsPaul J Stoffel
Original AssigneeMonsanto Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Oxamyl chloride substituted carbamates
US 3539618 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,539,618 OXAMYL CHLORIDE SUBSTITUTED CARBAMATES Paul J. Stoifel, St. Louis, Mo., assignor to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 310,847, Sept. 23, 1963. This application Apr. 15, 1966,

Ser. No. 542,749

Int. Cl. C07c 103/32 US. Cl. 260-471 7 Claims ABSTRACT OF THE DISCLOSURE Carbamides of the formula wherein R is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl having up to four substituents, wherein the hydrocarbyl is selected from the group consisting of primary alkyl of not more than 12 carbon atoms, benzyl and phenyl, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, chlorine, bromine, alkoxy of not more than 4 carbon atoms, alkyl of not more than 4 carbon atoms and phenyl; and R is selected from the group consisting of hydrocarbyl and substituted hydro carbyl having up to four substituents, wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, cycloaliphatic having at least 4 and not more than 8 carbon atoms, benzyl and phenyl, and wherein the substituents on the hydrocarbyl are selected from the group consisting of chlorine, bromine, nitro, alkyl of not more than 4 carbon atoms, alkoxy of not more than 4 carbon atoms and phenyl are useful in the control of plant systems and pathogenic microorganisms.

This application is a continuation-in-part of application Ser. No. 310,847, filed Sept. 23, 1963, now abandoned.

This invention relates to novel carbamides and to processes for their preparation. The carbamides of this invention have biological toxicant properties and can be used r to control the growth of plant systems and to control pathogenic microorganisms.

The carbamides of this invention are prepared by a process which comprises reacting an N-substituted car bamic acid ester with oxalyl chloride in accordance with r the following representative synthesis:

consisting of nitro, chlorine, bromine, alkoxy of not more than 4 carbon atoms, alkyl of not more than 4 carbon atoms and phenyl; and R is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl having up to four substituents, wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, cycloaliphatic having at least 4 and not more than 8 carbon atoms, benzyl and phenyl, and wherein the substituents on the hydrocarbyl are selected from the group consisting of chlorine, bromine, nitro, alkyl of not more than 4 carbon atoms, alkoxy of not more than 4 carbon atoms and phenyl.

The process of this invention by which the carbamides are prepared involves reacting oxalyl chloride with a substantially equimolar amount of an N-substituted carbamic acid ester of the defined configuration. The N-substituents can vary widely but the esterifying group must be one of the narrower scope to eliect the formation of the new compounds. The reaction is conducted in an inert aromatic solvent medium, for example benzene, xylene, toluene, chloroxylene, chlorotoluene, 1,4-dichlorobenzene and other aromatic and halogen substituted aromatic hydrocarbons. The reaction mixture should be heated but temperatures as low as about 30 C. will effect a useful result. Higher temperatures, for example the reflux temperature of the chosen solvent medium, produce preferred rates of reaction. Temperatures as high as about C. will be useful; however, decomposition of the product takes place if this temperature is exceeded.

When the reaction has been completed or has proceeded to a desired extent, the product can be separated from the solvent medium by the addition of a suitable non-solvent which is miscible with the solvent medium, for example n-hexane or any other aliphatic petroleum fraction. This reduces the solubility of the product in the solvent medium and causes precipitation of the product. The reduction in temperature also aids in the separation of the desired product. The solid product can be separated by filtration and purified, if desired, by recrystallization from a suitable solvent, for example acetone.

Further details of the procedure and the novel compounds so prepared are set forth in the following examples.

EXAMPLE 1 A solution of 22 grns. of methyl 3,4-dichlorocarbanilate and 12.7 gms. of oxalyl chloride in 50 ml. benzene was heated at reflux temperature for six hours. The product N- 3,4-dichlorophenyl -N-carbomethoxyoxamyl chloride was separated from the benzene by the addition of 200 ml. of hexane to the cooled solution. Upon recrystallization from toluene white platelike crystals (M.P. 100.4 to 1012 C.) were formed.

EXAMPLE 2 The procedure of Example 1 was repeated except that ethyl 3,4-dichlorocarbanilate was used in place of the methyl ester. The resulting product (M.P. 102-l03 C.) was found to have the structure i til-O-CH2-CH:

3 EXAMPLE 3 The reaction product of oxalyl chloride and n-propyl 3,4-dichlorocarbani1ate was found to have a melting point of 5657 C. and the structure The phenyl ester of N-allylcarbarnic acid was heated with oxalyl chloride in a toluene solution. The resulting product was found to have the structure:

Q oo CH2=CHCHz-N GGC1 II I! O 0 EXAMPLE 5 Benzyl N-ethylcarbamate was heated at reflux tempera ture with oxalyl chloride in a 1,4-dichlor0benzene solution. After refluxing for three hours the product was identified as that of the structure:

HaQz-N arr- 0 6 EXAMPLE 6 Using the procedure of Example 1 oxalyl chloride was reacted with phenyl N-3,4-dichlorocarbanilate in a xylene solution. Heating at reflux temperature for four hours produced a reaction mixture which upon cooling and dilution with n-hexane produced a product of the structure:

C-(fi-Cl o 0 EXAMPLE 7 The reaction at reflux temperature in a chlorotoluene solution between oxalyl chloride and Z-ethylhexyl carbanilate produced a product of the structure:

EXAMPLE 8 Using the procedure of Example 1 except that n-butyl N-cyclohexylcarbamate was used in place of the methyl 3,4-dichlorocarbanilate. The product was identified as N-carbobutoxy-N-cyclohexane oxamoyl chloride,

EXAMPLE 9 In a toluene solution oxamyl chloride and N-benzyl n-propylcarbamate were heated at 115 C. for 16 hours. The product was identified as N-benzyl-N-carbon-n-propoxy oxamyl chloride.

EXAMPLE A xylene solution containing equal mols of oxalyl chloride and N-ethylmethylcarbamate was heated at reflux for 10 hours. The product was identified as having the structure:

ll II Useful compounds may also be prepared by reacting oxalyl chloride with other esters of N-substituted carbamic acids by the procedures above described to obtain the following:

O G H2---- 0 H3 Although the invention has been described with respect to specific modifications, it is not intended that the details thereof shall be limitations on the scope of the invention except to the extent incorporated in the following claims.

What is claimed is:

1. Compound of the formula II 0-0 B wherein R is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl having up to four substituents, wherein the hydrocarbyl is selected from the group consisting of primary alkyl of not more than 12 carbon atoms, benzyl and phenyl, and wherein the substituents on the hydrocarbyl are selected from the group consisting of nitro, chlorine, bromine, alkoxy of not more than 4 carbon atoms, alkyl of not more than 4 carbon atoms and phenyl; and R is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl having up to four substituents, wherein the hydrocarbyl is selected from the group consisting of alkyl of not more than 12 carbon atoms, alkenyl of not more than 12 carbon atoms, cycloaliphatic having at least 4 and not more than 8 carbon atoms, benzyl and phenyl, and wherein the substituents on the hydrocarbyl are selected from the group consisting of chlorine, bromine, nitro, alkyl of not more than 4 carbon atoms, alkoxy of not more than 4 carbon atoms and phenyl.

2. Compound of claim 1 wherein R is primary alkyl of not more than 12 carbon atoms.

3. Compound of claim 1 which is N-3,4-dichlorophenyl- N-carbomethoxy oxamyl chloride.

4. Compound of claim 1 which is N-benzyl-N-carbo-npropoxy oxamyl chloride.

5. Compound of claim 1 which is N-ethyl-N-carbobenzoxy oxamyl chloride.

6. Compound of claim 1 which is N-(n-propyl)-N- carbophenoxy oxamyl chloride.

7. Compound of claim 1 which is N-ethyl-N-carboxymethoxy oxamyl chloride.

6 References Cited Compt. Rend. by Najer et 211., vol. 242 (1956), pages 2727-2729 relied on.

LORRAINE A. WEINBERGER, Primary Examiner L. A. THAXTON, Assistant Examiner US. Cl. X.R.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3178470 *Dec 14, 1962Apr 13, 1965Monsanto CoN-(aryl)oxamates
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4116668 *Oct 3, 1977Sep 26, 1978Stauffer Chemical CompanyN-carbamoyl ethyl oxanilates
US4402734 *Oct 17, 1973Sep 6, 1983Sumitomo Chemical Co., Ltd.Herbicidial composition and method
EP0113317A1 *Dec 19, 1983Jul 11, 1984Ciba-Geigy AgCarbamates
EP0138181A2 *Oct 8, 1984Apr 24, 1985Bayer AgN-oxalyl derivatives of n-methyl carbamates, process for their preparation and their use as pesticides
Classifications
U.S. Classification560/30, 504/302, 560/161, 560/163, 560/137, 560/22, 560/115
International ClassificationC07C271/06
Cooperative ClassificationC07C271/06
European ClassificationC07C271/06